DE2015434A1 - New copolymers, processes for their preparation and their uses - Google Patents

Description

PATENT LAWYERS -.

DR.-ING. BY KREISLER DR.-ING. SCHDNWALD 2 0 1 5 A 3 A DR.-ING. TH. MEYER DR. FUES DlPL.-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLÖPSCH

COLOGNE I, DEICHMANNHAUS

, March 51, 1970 Ke / Ax / Hz

MO NTECATINI EDISON S.p.A., Foro Buonaparte 31, Milan (Italy).

New copolymers, processes for their preparation and their uses.

The invention relates to quaternary ethylene-propylene-butadiene-dicyclopentadiene copolymers and a process for their preparation with the aid of catalysts of the Ziegler-Natta type.

The applicant's Italian patent specification 64-9,768 describes the copolymerization of ethylene, propylene and dicyclopentadiene and the copolymers obtained in this way These copolymers were found to be vulcanizable by conventional methods, but their vulcanization rate is not fast enough. .

Italian patents 566 913, 664-769 and 664 770 of the applicant describe the copolymerization of ethylene, propylene and butadiene as well as those obtained here Copolymers. These copolymers were also found to be vulcanizable by customary processes, but are the mechanical and elastic properties the vulcanizates loaded with reinforcing fillers worse than those of other reinforced vulcanizates. For example, their properties were found to be inferior to the properties of the reinforced ones

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Vulcanizates made from the ithylon-propylene-dicyclopentadione copolymers can be obtained.

It has now surprisingly been found that the above Nnxhteile mentioned can be avoided if a during the production of the elastomers mentioned Butadiene-dicyclopentadiene-genetically used as a comonomer will.

If this mixture consists predominantly of dicyclopentadiene, it is possible to significantly increase polymer yields to increase the yields for the ethylene-propylene-butadiene copolymerization process are typical. Furthermore, the polymers obtained show a high vulcanization rate, the one with the rate of vulcanization for example an ethylene-propylene-ethylidene norbornene copolymer is quite comparable.

The ethylene-propylene-butadiene-dicyclopentadiene copolymers according to the invention are manufactured by processes described in the aforementioned Italian patents are described by the applicant. In detail, this polymerization is carried out using catalysts carried out, which are preferably soluble and well dispersed in the polymerization medium, contain halogens and formed by converting the following compounds:

a) hydrides or organometallic compounds of beryllium, aluminum or lithium-aluminum, e.g. beryllium dialkyls, Aluminum trialkyls, lithium aluminum tetralkyls, Beryllium alkyl chlorides, aluminum alkyl chlorides (or mono-, di- or sesquichlorides), aluminum phenyl bromides, Lithium aluminum monofluorotrialkyls and beryllium phenylodide.

b) Vanadium compounds that are soluble in hydrocarbons, e.g. vanadium halides and oxyhalides, Vanadium and vanadyl alcoholates and acetylacetonates

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and complexes made from vanadium halides !! and oxyhalides can be obtained with Lewis BRses.

Preference is given to catalysts in which at least one of components a) or b) at least one halogen atom

contains. .

The copolymerization is carried out at temperatures between -80 ° and + 125 ° C, but preferably between -30 ° and +30 ⁰ C, since the above-mentioned catalysts in dieeem area exhibit a higher activity and stability.

The polymerization is in the liquid phase in the presence or absence of solvents for the copolymers formed. Suitable solvents are i

for example aliphatic, aromatic and cycloaliphatic hydrocarbons. Chlorinated hydrocarbons can also be used are used that are not reactive with the catalysts used, e.g. * chlorobenzene, Tetrachlorethylene and methyl chloride.

When working without a solvent, the liquid polymerization medium consists predominantly of a ^ Ethylen-propylen-Geraisch, in which the formed copolymers is insoluble. In this case the polymerization proceeds eonit in "suspension · * · To make copolymers with very homogeneous To obtain the composition, it is necessary to determine the ratio between the concentrations of the four monomers | in the liquid polymerization medium throughout Course of the. Keep polymerization constant.

By changing these ratios, the composition of the copolymers can be varied within a wide range. To achieve amorphous copolymers which contain less than 85 M0I / S ethylene, an ethylene / propylene molar ratio between At 200 and 1: 4 is preferred *

When working with ratios greater than 1: 1, generally formed copolymers, which for poly-

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BAD ORJQINAt

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ethylene show typical crystallinity. The preferred propylene content is between 50 and 15 mol. The propylene content, based on the sum of the two dienes, is between 0.1 and 20 Mo 1-%.

The preferred molar ratio between butadiene and dicyclopentadiene in the copolymers formed is between 5 * 1 and 1: 5 », however, it is easy to vulcanize also achievable with copolymers in which this ratio is between 1:10 and 10: 1.

The copolymers according to the invention have a linear structure, i.e. they do not contain long branches, recognizable by the fact that they have practically the same properties, in particular the same viscosity behavior have as known linear ethylene-propylene copoly mers.

The molecular weights of the copolymers according to the invention Bind generally higher than 20,000, i.e. their intrinsic viscosity is above 0.5 dl / g, determined in tetrahydronaphthalene at 135 ° C (or in toluene at 30 ° C).

If the double bond content is higher than 0.4, the copolymers produced can be converted to conventional vulcanization processes, e.g. with sulfur, accelerators and soot, vulcanize lightly. Some Vulkanisationsgeechwindigkeiten are reasonable in the following examples W give. These examples further illustrate that the vulcanized copolymers have excellent physical, chemical and dynamic properties which are fully comparable to the properties of the best ethylene-propylene-ethylidene-norbornene copolymers.

On the basis of these properties, the copolymers are found according to of the invention in all fields in which natural rubber and other synthetic rubbers are used as they can easily replace the latter.

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BATH ORIGINAL

Example 1.

The reaction apparatus consists of a glass cylinder, the a diameter of 8 cm and a fit of of 3000 ml and is provided with a stirrer, thermometer and inlet and outlet pipe for the gases « The inlet pipe for the gases is to the bottom of the Reactor out and ends in a Pritten disc.

In the reactor, which is made by immersion in a temperature bath is kept at 5 ° C, 15OO snl of toluene and 2 ml Cyclopentadiene introduced. Through the gas inlet pipe a mixture of propylene, ethylene and butadiene is introduced into the reactor. These three monomers are in the following Quantities circulated:

Propylene 4-50 1 / hour

Ethylene 300 l / h '

Butadiene 2 1 / hour

After a saturation time of 30 minutes, 6 mmol of Al ₂ (CpH ₁ -), Cl- and 0.15 mmol of vanadium triacetylacetonate are added as a solution in 10 ml of toluene to the reactor. During the experiment, the gaseous propylene-ethylene-butadiene mixture is continuously fed in and discharged. After 60 minutes, calculated from the introduction of the catalyst, the polymerization is terminated by adding 10 ml of methanol. The product is cleaned in a separating funnel by washing several times with dilute hydrochloric acid and then with water and finally coagulated with an acetone-methanol mixture. After drying under reduced pressure, 24.5% of a solid product is obtained which is X-ray amorphous, looks like an unvulcanized elastomer - and is completely soluble in boiling n-heptane.

The infrared analysis shows that the product is 43 wt .-% of propylene, 2 wt -.% Butadiene and 3 wt -. ° / a dicyclopentadiene contains. It has a Mooney viscosity (MM- at 100 ° C) of 98.

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100 parts by weight of the copolymer are mixed with 80 parts by weight of ISAF carbon black, 55 parts by weight of "Plexon 766" oil, 1 part by weight of stearic acid, 5 parts by weight of zinc oxide, 0.75 parts by weight. Parts of mercaptobenzothiazole, 1.5 parts by weight of tetramethylthiuram monosulfide and 1.75 parts by weight of sulfur are mixed. The mixture is vulcanized for different ^{times at 150 ° C. in a press.} The properties of the vulcanizates are given in the table below.

Vulcanization time, min. Tensile strength, kg / cm elongation at break, %

t modulus of elasticity in "kg / cm ²

at 2OO? 4 elongation

at 300% elongation, deformation rest, % Goodrich ΔT index, ⁰ G

"The Goodrich Δ T index in this example and in the following examples was measured by a Goodrich flexometer according to ASTM 623 is determined (25 minutes at 100 ⁰ O, stroke 4.445 now at 1800 cycles / minute, load the sample 10.01 kg / cm; diameter of the sample 1.78 cm; height of the sample 2.54 cm).
Example 2

15th 30th 60 90 120 180 240 30th 232 218 216 214 207 202 80 580 520 520 510 500 480 32 42 50 50 50 50 54 69 84 98 97 100 100 100 36 28 20th 18th 16 16 16 26th

The experiment described in Example 1 was repeated, but with the addition of butadiene in an amount of 1 l / hour. This gave 28 g of an amorphous polymer, the 42 wt. .% Containing butadiene and had a Mooney viscosity of 120 - propylene, 3 »4 wt -.% Dicyclopentadiene and 0.4 wt.

The copolymer was in the same mixture and under the same conditions as described in Example 1, vulcanized. The properties of the vulcanizates are given in the following table:

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Vulcanization time, min. 15 30 60 90 120 180 Tensile strength, kg / cm ² 206 242 242 230 2JO 239 Elongation at break, % 800 640 500 460 450 460 Modulus of elasticity in
kg / cm ²

at 200% elongation

Hei 3009 * elongation
FormKnderunfrsrest, %
Goodrich AT Index, ^c

The experiment described in Example 2 was repeated. Here, 32 g of a polymer obtained, 42 wt .-% of propylene, 3 wt .-% of dicyclopentadiene and 0.4 wt -.% Containing butadiene and had a Mooney viscosity of 133.

The copolymer was vulcanized in the same mixture and under the same conditions as described in Example 1. The properties of the vulcanizates are given in the following table:

19th C. 40 5 * 60 65- 63 65 37 example 78 112 120 122 125 125 40 22nd 16 12th 12th 12th 12th 22nd

Vulcanization time, min, . 15th 30th 4th 60 90 120 180 ** 240 Tensile strength, kg / cm 215 248 248 224 228 242 240 Elongation at break, % 860 680 5 * 0 480 460 460 460 Young's modulus in kg / cÄ ² at 200% elongation 19th 32 52 53 "5 *. 59 64 at 3QQ & elongation 3β 64 101 109 113 128 124 Fora change remainder, % 42 24 18th 14th 14th 14th 14th Goodrich AT-iIndex, ⁰ C 21st example

The experiment described in Example 1 was repeated, but / hr, this was in an amount of 0.5 1 under the supply of butadiene, 35 g of a product are obtained, dan 4-1 drinks .- $ propylene, 2.6 wt -. & Dicyclopentadiene and 0 _t 15 wt .- ^> butadiene and had a Mooney viscosity ▼ on IT *.

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BATH ORIGINAL

The copolymer was in the same blend and under the same conditions as described in Example 1, vulcanized. The properties of the vulcanizates are in in the following table.

Vulcanization time, min, 198 30th 5 60 90 120 180 240 Tensile strength, kg / cm " 780 269 271 255 252 245 257 Elongation at break, % 670 580 500 480 460 480 Young's modulus in
kg / cm ^
at 2OO # elongation 17th at 300% elongation 37 34 45 53 52 56 62 Deformation rest, % 36 65 95 112 113 124 130 Goodrich AT Index ⁰ C 24 18th 12th 12th 12th 10 example 19th

The experiment described in Example 1 was repeated, but using 0.7 ml of dicyclopentadiene. Here 19 »6 g of a polymer were obtained which contained 39% by weight Propylene, 2.8% by weight butadiene and 0.7% by weight dicyclopentadiene and had a Mooney viscosity of 102.

The copolymer was in the same mixture and under the same conditions as described in Example 1, vulcanized. The properties of the vulcanizates are given in the following table:

»Ulcanization time, min. 15th 30th 60 90 120 240 Tensile strength, kg / cm 204 240 218 227 231 213 Elongation at break, % 680 640 560 570 590 540 Young's modulus in kg / cm ² at 200% elongation 28 39 41 43 40 41 at 300 # elongation 59 83 82 91 85 86 Pour change remainder, % 36 30th 24 20th 22nd 20th Goodrich AT Index ⁰ C 30th

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Example 6

Ethylene, propylene and butadiene were copolymerized in the manner described in Example 1, the butadiene being supplied in an amount of 4 l / hour. This gave 20 g of a product which contained 39% by weight of propylene and 4% by weight . containing% butadiene and had a Mooney viscosity of 93 - wt.

The copolymer was in the same blend and under vulcanized under the same conditions as described in Example 1. The properties of the vulcanizates are in in the following table: -

Vulcanization time, min. 15th 30th 60 90 120 180 240 ρ
Tensile strength, kg / cm 206 209 212 189 18? 181 190 Elongation at break, % 680 620 630 590 580 580 580 Modulus of elasticity in kg / cm ^ at 20CP / 0 elongation 30th 33 33 35 37 36 35 at 300% elongation 58 67 71 68 71 66 70 Deformation rest, % 42 30th 32 30th 30th 26th 28 Goodrich AT Index, ° C 38

The above values show that the polymer yields and the properties of the vulcanizates are worse than in the experiment described in Example 2.

Example 7

Ethylene, propylene and butadiene were copolymerized in the manner described in Example 6, except that the butadiene was supplied in an amount of 2 l / hour. Here, 23.5 g of a polymer obtained, from 4 to 0.5 wt .-% of propylene and 2.4 wt -% of butadiene contained.. This copolymer was vulcanized in the same mixture and under the same conditions as described in Example 1. The properties of the vulcanizates are given in the table below.

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Vulcanization time, I. ^T in. 15 50 60 90 120 180 240 Tensile strength, kg / cm ² .130 200 184 185 187 176 171 Elongation at break,: 'o 700 640 600 600 600 580 580

Modulus of elasticity in kg / cm2

at 200? S elongation

at 30050 elongation deformation rest, % Goodrich ΔΤ index, ⁰ G

28 32 34 35 35 34 37 56 63 67 69 67 65 68 50 40 32 32 32 34 32

The above values show that the polymer yields and the properties of the vulcanizates are worse than those of the ethylene-propylene-butadiene described in Example 2 en-dicyclopentadiene copolymers.

Example 8

An ethylene-propylene-dicyclopentadiene copolymer which Contained 32 wt .-% propylene and 3.9 wt .-% dicyclopentadiene and had a Hooney viscosity of 163, was in the same mixture and under the same conditions, as described in Example 1, vulcanized. The properties of the vulcanizates are given in the table below called:

Vulcanization time, min,

Tensile strength, kg / cm elongation at break, % modulus of elasticity in kg / cm ^

at 200% elongation

deformation rest at 300% elongation, %

The above values show that the rate of vulcanization is lower than in the case of the ethylene-propylene-butadiene-dicyclopentadiene copolymers described in Examples 1 to 5. 90? Lbs of the maximum modulus of elasticity at 3OO - 3 elongation were only after a vulcanization period reached in 120 minutes.

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30th 60 90 120 180 240 245 207 199 182 192 195 640 480 430 400 400 390 35 52 59 65 69 65 69 101 118 124 133 135 28 16 12th 12th 8th 8th

Example 9

The experiment described in Example 2 was repeated using 0.1S mmol VOCl. Here, 20 g of an amorphous Pol2 ^r mers obtained which 39 wt .-% propylene, 3.8 wt, -% of dicyclopentadiene and 0.3 part by weight 9 contained »butadiene and had a Mooney viscosity of 86th

The copolymer was in the same mixture and under the same conditions as described in Example 1, vulcanized. The properties of the vulcanizates are given in the table below.

Vulcanization time, min. . 15th 30th 10 60 90 120 240 Tensile strength, kg / cm 201 248 243 243 245 231 Elongation at break, % 780 640 500 460 440 420 Young's modulus in kg / cra ² at 200 # elongation 24 44 63 75 74 78 at 300% elongation 43 80 117 136 137 140 . Deformation rest, % 48 28 16 14th 14th 12th Ooodrich AT Index, ⁰ C 26th example

Ethylene, propylene and butadiene were under the conditions described in Example 7, but using Clay 0.15 raMol VOCIx copolymerized - 13 g obtained a polymer containing 37 wt .- # propylene and Contained 2.7% by weight of butadiene and had a Mooney viscosity ▼ on had 60.

The copolymer was vulcanized in the mixture described in Example 1 at 150 ° C. for 60 minutes. This gave a volcanic acid with the following properties: tensile strength 158 kg / cm ²

Elongation at break 630 %

Modulus of elasticity at 200 * elongation 32 kg / cm ² Modulus of elasticity at 300 # elongation 55 kg / cm residual deformation 48 %

Goodrich AT index above 50 ⁰ C

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BATH ORIGINAL

Claims (1)

Claims 1) High molecular weight unsaturated copolymers of ethylene, propylene, 1,3-butadiene and bicycle- ^ which can be vulcanized with sulfur pentadiene. 2) copolymers according to claim 1 with one in tetrahydronaphthalene at 135 ° C determined intrinsic viscosity of more than 0.5 dl / g. fc 3) Copolymers according to Claims 1 and 2, containing 15 to 50 Mole # propylene units and 0.1 to 20 mole # total diene units. 4) Copolymers according to Claim J>, containing at least 0.4 MoI-Ji unsaturation sites. 5) Copolymers according to claim 1 to 4, containing butadiene and dicyclopentadiene units in a molar ratio between 10: 1 and 1:10, preferably between 5 s 1 and 1: 5 6) copolymers according to claim 1 to 5 »characterized in that that they contain less than 85 mol # ethylene units w and are amorphous when examined by X-rays. 7) copolymers according to claim 1 to 6, characterized by a higher vulcanization rate than ethylene-propylene-Dlcyclopentadiene copolymers when vulcanizing in conventional sulfur-containing mixtures. 8) Use of copolymers according to claims 1 to 7 in optionally filler-containing mixtures containing sulfur or sulfur-releasing compounds as crosslinking vulcanization accelerators included, for the production of 009841/1840 vulcanized elastomers. 9) A method for producing products according to claim 1 to 8, characterized in that ethylene, propylene, 1,3-butadiene and dicyclopentadiene at temperatures in the range between -8o ° and + 125 ° C in the presence of a catalyst system a) at least one organometallic compound or a hydride of beryllium, aluminum or lithium-aluminum and · b) at least one vanadium compound soluble in hydrocarbons indüng copolymerized and the copolymers obtained in this way if necessary vulcanized. 10) Method according to claim 9j, characterized in that one as component a) of the catalyst system aluminum trialkyls or aluminum alkyl halides are used. 11) Method according to claim 9, characterized in that as component a) of the catalyst system, aluminum ethyl sesquichloride used. ' 12) Method according to claim 9 to 11, characterized in that that as component b) of the catalyst system vanadium halides, vanadium oxyhalides, vanadium or vanadyl alcoholates, Vanadium or vanadyl halogen alcoholates, vanadium or vanadyl acetylacetonates or vanadium or Vanadyl haloacetylacetonate used. . · Process according to Claims 9 to 11, characterized in that complex compounds are used as component b) of the catalyst system from vanadium halides or oxyhalides 009841/1840 used with Lewis bases. Method according to Claims 9 to Ij5, characterized in that that a catalyst system is used in which at least one component contains halogen. 15) The method of claim 9 to l4, characterized in that the copolymerization is conducted at temperatures ranging between -30 ° and + 3O ⁰ C performs. 16) Method according to claim 9 to 15, characterized in that that the copolymerization is carried out in the liquid phase and in the absence of a solvent for the copolymer formed performs. 17) Method according to claim 9 to 15, characterized in that that the copolymerization in the liquid phase and in the presence of a solvent for the copolymer formed performs. 18) Method according to claim 17, characterized in that the solvent for the copolymers compared to the Catalyst system inert chlorinated hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons or their mixtures are used. 19) Method according to claim 9 ° is 18, characterized in that that with a molar ratio between ethylene and propylene in the liquid polymerization phase in the range between 1: 200 and 1: 4 works. 009841/1840